RU2504563C2 - Fire-resistant compositions with modified impact strength made from polyalkylene terephthalate/polycarbonate - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: moulded article contains a moulding composition with modified impact strength, which includes an aromatic polycarbonate, polyalkylene terephthalate, a rubber-modified graft copolymerisate and a phosphinic acid salt of general formula

, where M^m+ is a metal cation.

EFFECT: invention enables to obtain compositions with modified impact strength, having high heat resistance, good fire resistance and high modulus of elasticity.

17 cl

Description

The present invention relates to compositions with modified impact resistance of polyethylene terephthalate / polycarbonate that contain a phosphinic acid salt, the use of these compositions with modified impact strength of polyethylene terephthalate / polycarbonate for the manufacture of molded products, as well as the molded products themselves.

International application WO-A 2005/044906 proposes thermoplastic molding compositions containing at least one metal salt of hypophosphoric acid and at least one aromatic polycarbonate resin, as well as its mixture with a styrene-containing resin from a grafted copolymer with a rubber fraction of 5-15 % The proportion of styrene-grafted grafted copolymer is 10-40% of the mass. The obtained molding materials are characterized by good fire resistance, high thermal stability under processing conditions, as well as good weather resistance. Due to the low rubber content, other characteristics, especially mechanical properties, are low.

In the international application WO-A 1999/57192 describes thermoplastic molding materials containing 5-96% of the mass. complex polyester or polycarbonate, 1-30% of the mass. salts of phosphinic acid, and / or salts of diphosphinic acid, and / or their polymers, 1-30% of the mass. at least one organic phosphorus-containing flame retardant, as well as other suitable additives.

In the German patent application DE-A 102004049342, thermoplastic molding compounds are proposed containing 10-98% by weight. thermoplastic polymer, 0.01-50% of the mass. highly branched polycarbonate, or highly branched polyester, or mixtures thereof, 1-40% of the mass. a halogen-free flame retardant selected from the group of phosphorus-containing or nitrogen-containing compounds, or a condensed product containing phosphorus and nitrogen, or mixtures thereof, as well as other suitable additives.

In German patent application DE-A 19904814 describes thermoplastic molding materials containing 20-98% of the mass. complex polyester, 1-50% of the mass. polycarbonate, 1-40% of the mass. salts of phosphinic acid and / or salts of diphosphinic acid and / or their polymers, as well as other suitable additives.

Japanese Patent Application JP-A 2001-335699 describes flame retardant resin compositions containing two or more thermoplastic resins selected from the group of styrene resins, aromatic polyesters, polyamide resins, polycarbonate resins and polyphenylene ether resins as well as one or more (non) organic salts of phosphinic acid, as well as other suitable additives.

Japanese Patent Application JP-A 2001-261973 (Daicel Chemical Industries Ltd.) describes compositions of thermoplastic resins and (in) organic salts of phosphinic acid. An example is a combination of polybutylene terephthalate (PBT), calcium phosphinate, and polytetrafluoroethylene (PTFE).

Japanese Patent Application JP-A 2002-161211 proposes compositions of thermoplastic resins and flame retardants, such as salts of phosphinic and phosphoric acids, as well as their derivatives. An example is a combination of polybutylene terephthalate (PBT), a copolymer of acrylonitrile, butadiene and styrene (ABS), polyoxyphenylene, calcium phosphinate, organic phosphate, and fiberglass.

According to prior art, conventional aromatic flame retardants for polyethylene terephthalate / polycarbonate compositions are organic, aromatic phosphates. These compounds can be low molecular weight, presented as mixtures of various oligomers or as mixtures of oligomers with low molecular weight compounds (for example, as in international applications WO-A 99/16828 and WO-A 00/31173). Good efficiency as a fire retardant is prevented by the lack of a strong plasticizing effect of these compounds on the polymer components, so that the heat resistance of these molding materials is unsatisfactory for many applications.

The objective of this invention is the provision of compositions with modified impact strength of polyethylene terephthalate / polycarbonate, having the optimal combination of high heat resistance, good fire resistance, and excellent mechanical properties (in particular, a higher elastic modulus E).

Thus, it was unexpectedly found that molding materials, or compositions containing polycarbonate A), polyalkylene terephthalate B), rubber-modified grafted copolymerizate C), as well as phosphinic acid salt D), have the desired property profile.

Thus, it was unexpectedly found that the solution to the above technical problems are compositions containing:

A) from 41 to 97 mass. parts, preferably from 57 to 93 mass. parts, particularly preferably from 64 to 83 mass. parts (in each case, in terms of the sum of the mass parts of components A + B + C + D) of aromatic polycarbonate,

B) from 2 to 19 mass. parts, preferably from 4 to 17 mass. parts, particularly preferably from 7 to 15 mass. parts (in each case, in terms of the sum of the mass parts of components A + B + C + D) of polyalkylene terephthalate,

C) from 0.5 to 15 mass. parts, preferably from 2 to 11 mass. parts, particularly preferably from 5 to 9 mass. parts (in each case, in terms of the sum of the mass parts of components A + B + C + D) of the grafted copolymer modified with rubber,

D) from 0.5 to 25 mass. parts, preferably from 1 to 15 mass. parts, particularly preferably from 7 to 12 mass. parts (in each case, in terms of the sum of the mass parts of components A + B + C + D) salts of phosphinic acid,

E) from 0 to 20 mass. parts, preferably from 1 to 15 mass. parts (provided that the sum of the mass parts of the components A + B + C + D = 100) vinyl (co) polymerizate that does not contain rubber,

F) from 0 to 50 mass. parts, preferably from 0.5 to 25 mass. parts (in each case, provided that the sum of the mass parts of the components A + B + C + D = 100) additives,

moreover, all data on mass parts in the submitted application are normalized in such a way that the sum of the mass parts of the components A + B + C + D in the composition is 100.

Too high a content of component B) (i.e. 20 parts by mass or more) has the disadvantage that the fire retardant properties no longer satisfy the established requirements.

Component A

As component A), the compositions of the invention described in the invention comprise polycarbonate or a mixture of polycarbonates. Preferred polycarbonates are such bisphenol-based homopolycarbonates and copolycarbonates of the general formula (I),

in which Z represents a divalent organic residue with the number of carbon atoms from 6 to 30, which contains one or more aromatic groups. Preferred are bisphenols of the general formula (Ia)

,

,

wherein

A is a single bond, alkylene containing from 1 to 5 carbon atoms, alkylidene containing from 2 to 5 carbon atoms, cycloalkylidene containing from 5 to 6 carbon atoms, -O-, -SO-, -CO-, -S -, -SO ₂ -, arylene containing from 6 to 12 carbon atoms, which may be fused to other aromatic rings, optionally containing heteroatoms, or is a residue of the general formula (II) or (III)

B, respectively, is an alkyl containing from 1 to 12 carbon atoms, preferably methyl, halogen, preferably chlorine and / or bromine,

x in each of the cases independently from each other is 0, 1 or 2,

p equals 1 or 0, and also

R ¹ and R ² for each X ¹ can be selected individually and independently from each other represent a hydrogen atom or alkyl containing from 1 to 6 carbon atoms, preferably a hydrogen atom, methyl or ethyl,

X ¹ is a carbon atom as well

m is an integer from 4 to 7, preferably 4 or 5, provided that at least one X ¹ atom, the substituents R ¹ and R ² are simultaneously alkyl.

Examples of bisphenols corresponding to the general formula (I); are bisphenols, which belong to the following groups: dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, indane bisphenols, bis (hydroxyphenyl) sulfides, simple bis (hydroxyphenyl) ether, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, as well as α, α'-bis (hydroxyphenyl) diisopropylbenzene.

Derivatives of the listed bisphenols, which can be obtained, for example, by alkylation or halogenation of aromatic rings of the named bisphenols, are also examples corresponding to the general formula (I).

Examples of bisphenols corresponding to the general formula (I) are, in particular, the following compounds: hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (3,5 -dimethyl-4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) p / m-diisopropylbenzene, 1,1- bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3-methylcyclohexane, 1,1-bis ( 4-hydroxyphenyl) -3,3-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -4-methylcyclohexane, 1,1-b is (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol-A), 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2 , 4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, α, α'-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m- diisopropylbenzene (so-called bisphenol-M), α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, as well as indanbisphenol.

Particularly preferred polycarbonates are bisphenol-A-based homopolycarbonate, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane-based homopolycarbonate, and copolycarbonates based on both bisphenol A and 1,1- monomers bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

The described bisphenols corresponding to the general formula (I) can be obtained by known methods, for example, from the corresponding phenols and ketones.

The aforementioned bisphenols, as well as the method for their preparation, are described, for example, in the monograph by N. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Band 9, pp. 77-98, Interscience Publishers, New York, London, Sidney, 1964, as well as in patent applications US-A 3028635, US-A 3062781, US-A 2999835, US-A 3148172, US-A 2991273, US-A 3271367, US-A 4982014, US-A 2999846, in German applications DE-A 1570703, DE-A 2063050, DE-A 2036052, DE-A 2211956, DE-A 3832396, as well as French patent application FR-A 1561518, as well as in Japanese open descriptions with the following application numbers: JP-A 62039 1986; JP-A 62040 1986; and JP-A 105 555 1986.

1,1-Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and its preparation are described, for example, in US patent application US-A 4,982,014.

Indanbisphenols and their preparation are described, for example, in US patent application US-A 3288864, Japanese patent application JP-A 60035150, as well as US patent application US-A 4334106. Indanbisphenols can be obtained, for example, from isoprenylphenol or its derivatives or from dimers of isoprenylphenol or its derivatives in the presence of a Friedel-Kraft catalyst in an organic solvent.

Polycarbonates can be obtained using known methods. Suitable methods for producing polycarbonates are, for example, production from bisphenols with phosgene by the method of interfacial polycondensation, or from bisphenols with phosgene by the method of polycondensation in solution, the so-called pyridine method, or from bisphenols with carbonic esters by the melt transesterification method. These production methods are described, for example, in the publication of H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Band 9, pp. 31-76, Interscience Publishers, New York, London, Sidney, 1964. These production methods are also described in D. Freitag, U. Grigo, PR Muller, N. Nouvertne, “Polycarbonates” in Encyclopedia of Polymer Science and Engineering, Volume 11, Second Edition, 1988, pages 648 to 718, as well as U. Grigo, K. Kircher und PRMuller “Polycarbonate” in Becker, Braun, Kunststoff-Handbuch, Band 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munchen, Wien 1992, pages 117 to 299, and also in DCPrevorsek , B.T. Debona und Y. Kesten, Corporate Research Center, Allied Chemical Corporation, Morristown, New Jersey 07960, Synthesis of Poly (estercarbonate) Copolymers ”in Journal of Polymer Science, Polymer Chemistry Edition, Vol. 19.75-90 (1980).

The melt transesterification method is specifically described, for example, in H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Band 9, pages 44-51, Interscience Publishers, New York, London, Sidney, 1964, as well as in German application DE-A 1031512.

In the preparation of polycarbonate, starting materials and auxiliary substances with a small degree of impurities are preferably used. In particular, when using the melt transesterification method, the bisphenols used and the carbonic acid derivatives used to the maximum extent should not contain alkali metal ions and alkaline earth metal ions. Starting materials of a purity of this kind can be obtained, for example, due to the fact that derivatives of carbonic acid, for example, a carbonic ester, as well as bisphenols, are recrystallized, washed or distilled.

Polycarbonates that are suitable according to the invention preferably have a weight average molecular weight (M _w ), which can be determined, for example, by ultracentrifugation or light scattering methods, ranging from 10,000 to 200,000 g / mol. Particularly preferably, they have a weight average molecular weight of from 12,000 to 80,000 g / mol, in particular, preferably from 20,000 to 35,000 g / mol.

The average molecular weight of the polycarbonates according to the invention can be regulated, for example, by a known method using an appropriate amount of chain terminating agent. Open chain agents can be used individually or as a mixture of various open chain agents.

Suitable chain terminating agents are both monophenols and monocarboxylic acids. Suitable monophenols are, for example, phenol, p-chlorophenol, p-tert-butylphenol, cumylphenol or 2,4,6-tribromophenol, as well as long chain alkyl phenols, such as, for example, 4- (1,1,3,3-tetramethylbutyl) phenol or monoalkylphenols or dialkylphenols containing a total of 8 to 20 carbon atoms in alkyl substituents, such as, for example, 3,5-ditretbutylphenol, p-tert-octylphenol, p-dodecylphenol, 2- (3,5-dimethylheptyl) phenol or 4 - (3,5-dimethylheptyl) phenol. Suitable monocarboxylic acids are benzoic acid, alkyl benzoic acids and halogen benzoic acids.

Preferred chain terminating agents are phenol, p-tert-butylphenol, 4- (1,1,3,3-tetramethylbutyl) phenol and cumylphenol.

The amount of chain terminating agent is preferably between 0.25 and 10 mol%, based on the amount of the corresponding bisphenol used.

Polycarbonates that are suitable according to the invention can be branched in a known manner, namely, preferably by the introduction of trifunctional or containing more than three functional groups of branching agents. Suitable branching agents are, for example, compounds with three or more phenolic groups or compounds with three or more carboxyl groups.

Suitable branching agents are, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, tri (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4-bis (4 -hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenylisopropyl) phenol, 2,6-bis (2-hydroxy-5'-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- ( 2,4-dihydroxyphenyl) propane, hex (4- (4-hydroxyphenylisopropyl) phenyl) terephthalic acid ester, tetra (4-hydroxyphenyl) methane, tetra (4- (4-hydroxyphene) or isopropyl) phenoxy) methane and 1,4-bis (4 ', 4' '- dihydroxytriphenyl) methylbenzene, as well as 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride, 3,3-bis (3-methyl-4-hydroxyphenyl ) -2-oxo-2,3-dihydroindole, trimesic acid trichloride and α, α ', α' '- tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene.

Preferred branching agents are 1,1,1-tris (4-hydroxyphenyl) ethane and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.

The amount of branching agent to be used if necessary is preferably from 0.05 mol%. up to 2 mol%, in terms of a mole of bisphenol used.

Branching agents can, for example, in the case of producing polycarbonate by the method of interfacial polycondensation, be loaded together with bisphenols and chain terminating agents in the aqueous alkaline phase or added dissolved in an organic solvent together with derivatives of carbonic acid. In the case of the transesterification process, the branching agents are preferably added together with dihydroxyaromatic compounds or bisphenols.

Preferred catalysts to be used in the preparation of polycarbonates by the melt transesterification process are ammonium salts and phosphonium salts known from the literature (see, for example, US Patent Application US-A 3442864, Japanese Patent Application JP-A-14742/72, US patent application US-A 5399659 and German patent application DE-A 19539290).

предпочтительно составляет от 10000 до 200000 г/моль, особенно предпочтительно от 20000 до 80000 г/моль (определяется с помощью гельхроматографии после предшествующей калибровки с применением светорассеяния или ультрацентрифугирования). Содержание ароматических карбонатных структурных единиц в блоксополимерах полидиорганосилоксанполикарбонат предпочтительно составляет от 75 до 97,5% масс., особенно предпочтительно от 85 до 97% масс. Содержание полидиорганосилоксановых структурных единиц в блоксополимерах полидиорганосилоксанполикарбонат предпочтительно составляет от 25 до 2,5% масс., особенно предпочтительно от 15 до 3% масс. Блоксополимеры полидиорганосилоксанполикарбонат могут быть получены, например, исходя из полидиорганосилоксанов, содержащих α,ω-бисгидроксиарилоксиконцевые группы, имеющих среднюю степень полимеризации, составляющую предпочтительно P_n = от 5 до 100, особенно предпочтительно P_n = от 20 до 80.Copolycarbonates may also be used. In the framework of this invention, copolycarbonates are primarily block copolymers of polydiorganosiloxane-polycarbonate, in which the mass-average molecular weight

preferably from 10,000 to 200,000 g / mol, particularly preferably from 20,000 to 80,000 g / mol (determined by gel chromatography after previous calibration using light scattering or ultracentrifugation). The content of aromatic carbonate structural units in the block copolymers of polydiorganosiloxane polycarbonate is preferably from 75 to 97.5% by weight, particularly preferably from 85 to 97% by weight. The content of polydiorganosiloxane structural units in block copolymers of polydiorganosiloxane polycarbonate is preferably from 25 to 2.5% by weight, particularly preferably from 15 to 3% by weight. Block copolymers of polydiorganosiloxane polycarbonate can be obtained, for example, starting from polydiorganosiloxanes containing α, ω-bis-hydroxyaryloxy-terminal groups having an average degree of polymerization, preferably P _n = 5 to 100, particularly preferably P _n = 20 to 80.

Polycarbonates can be mixed in the molten state or applied to the surface of conventional additives, such as, for example, a tool to facilitate removal from the mold. Preferably, the polycarbonates used already contain a means to facilitate removal from the mold before compounding with other components of the molding composition according to the invention.

Component B

As component B), the compositions according to the invention comprise one or a mixture of two or more different polyalkylene terephthalates. Polyalkylene terephthalates in the framework of this invention are Polyalkylene terephthalates, which are reaction products of terephthalic acid (or its reactive derivatives) and alkanediols, for example, based on propylene glycol or butanediol. According to the invention, as component B), preferably polyethylene terephthalate, polybutylene terephthalate and / or polytrimethylene terephthalate, most preferably polybutylene terephthalate, are used.

Polyalkylene terephthalates in the framework of this invention are the reaction products of aromatic dicarboxylic acids or their reactive derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or arylaliphatic diols, as well as mixtures of these reaction products.

Preferred Polyalkylene terephthalates can be obtained from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols containing from 2 to 10 carbon atoms, by known methods (Kunststoff-Handbuch, Bd. VIII, p. 695 onwards, Karl-Hanser- Verlag, Munchen 1973).

Preferred polyalkylene terephthalates contain at least 80, preferably at least 90 mol%, based on dicarboxylic acids, terephthalic acid residues, and also at least 80, preferably at least 90 mol%, based on the diol component, residues ethylene glycol and / or propanediol-1,3, and / or butanediol-1,4.

Preferred polyalkylene terephthalates, in addition to terephthalic acid residues, can contain up to 20 mol%, residues of other aromatic dicarboxylic acids with carbon atoms from 8 to 14 or aliphatic dicarboxylic acids with carbon atoms from 4 to 12, such as, for example, phthalic acid residues , isophthalic acid, naphthaline-2, b-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexane diacetic acid, cyclohexane dicarboxylic acid you.

Preferred polyalkylene terephthalates, in addition to residues of ethylene glycol, or propanediol-1,3, or butanediol-1,4, may contain up to 20 mol%. other aliphatic diols with the number of carbon atoms from 3 to 12 or cycloaliphatic diols with the number of carbon atoms from 6 to 21, for example, residues of propanediol-1,3, 2-ethylpropane-1,3-diol, neopentylglycol, 1,5- pentanediol, 1,6-hexanediol, cyclohexane-1,4-dimethanol, 3-methylpentane-2,4-diol, 2-methylpentane-2,4-diol, 2,2,4-trimethylpentane-1,3-diol, as well as 2-ethylhexane-1,6-diol, 2,2-diethylpropane-1,3-diol, 2,5-hexanediol, 1,4-di- (β-hydroxyethoxy) benzene, 2,2-bis- ( 4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis- (3-β-hydroxyethoxyphenyl) pro Pan, as well as 2,2-bis- (4-hydroxypropoxyphenyl) propane (German patent applications DE-A 2407674, 2407776, 2715932).

Polyalkylene terephthalates can be branched by the inclusion of relatively small amounts of 3- or 4-atomic alcohols or 3- or 4-basic carboxylic acids, such as those described, for example, in German patent application DE-A 1900270 and US patent application US US -PS 3692744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylol ethane and propane, as well as pentaerythritol.

It is advisable to use no more than 1 mol%. branching agent, calculated on the acid component.

Particularly preferred are Polyalkylene terephthalates, which were obtained only from terephthalic acid and its reactive derivatives (for example, its dialkyl esters such as dimethyl terephthalate) and ethylene glycol, and / or propanediol-1,3, and / or butanediol-1,4 (polyethylene - and polybutylene terephthalate), as well as mixtures of these polyalkylene terephthalates.

Preferred polyalkylene terephthalates are also copolyesters, which are obtained from at least two of the above acidic components and / or at least two of the above alcoholic components, especially (poly (ethylene glycol / butanediol-1,4) terephthalates.

Polyalkylene terephthalates typically have an intrinsic viscosity of from about 0.4 to 1.5 dl / g, preferably from 0.5 to 1.3 dl / g, measured respectively in the phenol / o-dichlorobenzene system (parts by weight 1: 1 ) at 25 ° C.

Preferably, the polyesters prepared according to the invention can also be used in admixture with other polyesters and / or other polymers. Mixtures of polyalkylene terephthalates with other polyesters are particularly preferably used.

Conventional polyesters can be blended into the polyesters in the molten state or applied to the surface, such as, for example, a mold release aid, stabilizers and / or a flow improver.

Component C

Component C includes one or more grafted copolymers of:

C.1 from 5 to 95% of the mass., Preferably from 30 to 90% of the mass. at least one vinyl monomer grafted onto

C.2 from 95 to 5 wt. -%, preferably from 70 to 10% of the mass. at least one graft copolymerization base selected from the following group: diene rubbers, ethylene-propylene- (diene) monomer rubbers (EP (D) M-rubbers) (i.e. rubbers based on an ethylene / propylene mixture, and if necessary diene), acrylate, polyurethane, silicone, silicone acrylate, chloroprene, as well as ethylene / vinyl acetate rubbers.

The graft copolymerization base C.2 typically has an average particle size (d ₅₀ value) of 0.05 to 10 μm, preferably 0.1 to 5 μm, particularly preferably 0.2 to 1 μm.

Monomers C.1 are preferably mixtures containing:

C.1.1 from 50 to 99 parts by weight of vinyl aromatic and / or core-substituted vinyl aromatic compounds (such as styrene, α-methyl styrene, p-methyl styrene, p-chlorostyrene) and / or (meth) acrylic acid alkyl esters with the number of atoms carbon in alkyl from 1 to 8 (such as methyl methacrylate, ethyl methacrylate), as well as C.1.2 from 1 to 50 mass. parts of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid alkyl esters with 1 to 8 carbon atoms in the alkyl, such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate and / or derivatives ( such as anhydrides and imides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenylmaleiminimide.

Preferred monomers C.1.1 are selected from at least one of the monomers styrene, α-methylstyrene and methyl methacrylate, preferred monomers C.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate. Particularly preferred monomers are styrene for C.1.1 and acrylonitrile for C.1.2.

Preferred bases for the grafted copolymerization of C.2 are silicone acrylate rubbers, diene rubbers (e.g. based on butadiene and isoprene) or a mixture of diene rubbers. Under the diene rubbers in the framework of this invention should also be understood copolymers of diene rubbers or mixtures thereof with other monomers capable of copolymerization (for example, the corresponding C.1.1 and C.1.2). As a rule, the bases for grafted copolymerization of C.2 have a glass transition temperature <10 ° C, preferably <0 ° C, particularly preferably <-10 ° C.

Particularly preferred polymerizates C are, for example, ABS polymers (emulsion, bulk or suspension ABS), such as those described, for example, in the open descriptions of German patents DE-OS 2035390 (= US patent US-PS 3644574) or DE- OS 2248242 (= GB-PS 1409275), or Ullmanns, Enzyklopadie der Technischen Chemie, "Bd. 19 (1980), page 280 ff. The gel content of the C.2 grafted copolymerization base is at least at least 20 wt. -%, in the case of bases for grafted copolymerization of C.2 obtained by the method of emulsions sion polymerization, preferably at least 40 wt.% (in toluene measurement).

Preferably, the grafted copolymerizate of components C.1 and C.2 has a core-shell structure, wherein component C.1 forms a shell (also referred to as a coating) and component C.2 forms a core (see, for example, Ullmann's Encyclopedia of Industrial Chemistry, VCH-Verlag, Vol. A21, 1992, page 635 and page 656).

The grafted copolymerizates C are obtained by the radical polymerization method, for example, using the methods of emulsion, suspension polymerization, solution or bulk polymerization, preferably by the method of emulsion polymerization and bulk polymerization.

Particularly suitable grafted rubbers are also ABS polymerizates, which are prepared by the emulsion polymerization process using redox initiation with an organic hydroperoxide and ascorbic acid initiator system according to US Pat. No. 4,937,285.

Since graft comonomers, as is known, do not necessarily completely enter the graft copolymerization reaction on the basis of the graft copolymerization reaction, according to the invention grafted copolymerizates C also mean those products obtained by (co) polymerizing grafted monomers in the presence of a graft copolymerization base and co-allocated during processing.

Suitable acrylate rubbers corresponding to C.2 of polymerizate C are preferably polymers from alkyl esters of acrylic acid, optionally containing up to 40% by weight, based on C.2, other ethylenically unsaturated monomers capable of polymerization. Preferred polymerizable acrylic esters include alkyl esters having from 1 to 8 carbon atoms in the alkyl, for example methyl, ethyl, butyl, n-octyl, and 2-ethylhexyl esters; haloalkyl esters, preferably haloalkyl esters with the number of carbon atoms in the alkyl from 1 to 8, such as chloroethyl acrylate, as well as mixtures of these monomers.

For polymer crosslinking, monomers containing more than one double bond capable of polymerization may be introduced into the copolymerization reaction. Preferred examples of monomers for polymer crosslinking are esters of unsaturated monocarboxylic acids containing from 3 to 8 carbon atoms, as well as unsaturated monohydric alcohols with carbon atoms from 3 to 12, or saturated polyols containing from 2 to 4 OH groups, and from 2 to 20 carbon atoms, such as ethylene glycol dimethacrylate, allyl methacrylate; multiply unsaturated heterocyclic compounds, such as trivinyl and triallyl cyanurates; polyfunctional vinyl compounds such as di- and trivinylbenzenes; as well as triallyl phosphate and diallyl phthalate. Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which contain at least three unsaturated ethylene groups. Particularly preferred crosslinking monomers are cyclic monomers triallyl cyanurate, triallyl isocyanurate, tri-acryloyl hexahydro-S-triazine, triallylbenzene. The amount of monomers for polymer crosslinking is preferably from 0.02 to 5% by weight, in particular from 0.05 to 2% by weight, based on the basis for the grafted copolymerization of C.2. In the case of cyclic crosslinking monomers containing at least three ethylenically unsaturated groups, it is advantageous to limit this amount to less than 1% of the mass. the amount of base for grafted copolymerization C.2.

Preferred "other" polymerizable ethylenically unsaturated monomers, which, if necessary, can serve as the basis for the graft copolymerization of C.2, along with esters of acrylic acid, are, for example, acrylonitrile, styrene, α-methyl styrene, acrylamides, vinylalkyl ethers with the number of carbon atoms in the alkyl from 1 to 6, methyl methacrylate, butadiene. Preferred acrylate rubbers as the basis for the grafted copolymerization of C.2 are emulsion polymerization products that have a gel content of at least 60% by weight.

Suitable silicone rubbers corresponding to C.2 can be obtained using the emulsion polymerization method, as, for example, described in US patents US 2891920 and US 3294725. Other suitable bases for grafted copolymerization corresponding to C.2, are silicone rubbers with active centers for graft copolymerization, such as those described in the open descriptions of German patents DE-OS 3704657, DE-OS 3704655, DE-OS 3631540, as well as DE-OS 3631539.

Silicone acrylate rubbers are also suitable as bases for the graft copolymerization of C.2 according to the invention. These silicone-acrylate rubbers are composite rubbers with active centers for grafted copolymerization, containing 10-90% of the mass. silicone rubber and from 90 to 10% of the mass. polyalkyl (meth) acrylate rubber, both of these rubber components in the composite rubber are interpenetrating, so that they basically cannot be separated from each other. If the proportion of the silicone-rubber component in the composite rubber is too high, then the finished resin compositions have unfavorable surface characteristics, as well as a deteriorated ability to stain. Conversely, if the proportion of polyalkyl (meth) acrylate rubber component is too high in the composite rubber, then this will adversely affect the impact strength of the finished resin compositions. Silicone-acrylate rubbers are known and are described, for example, in US Pat. No. 5,807,914, European Patent EP 430134, and also US Pat. No. 4,888,388. A grafted copolymer obtained by emulsion polymerization, which includes methyl methacrylate as C.1, and as C.2 silicone acrylate composite rubber.

The gel content of the C.2 graft copolymerization base is determined at 25 ° C in a suitable solvent (M. Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik I und II, Georg Thieme-Verlag, Stuttgart 1977).

The average particle size d ₅₀ is a diameter in which case 50% of the particles have a larger value and 50% a correspondingly smaller value. It can be determined using ultracentrifugation measurements (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-796).

Component D

Under the salt of phosphinic acid (component D) in the framework of the invention should be understood a salt of phosphinic acid with any metal cation. Mixtures of salts that differ in their metal cations can also be used. Metal cations are metal cations of the main subgroup of the 1st group (alkali metals, preferably Li ⁺ , Na ⁺ , K ⁺ ), the main subgroup of the 2nd group (alkaline earth metals; preferably Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , particularly preferably Ca ²⁺ ) or a main subgroup of the 3rd group (elements of the boron group; preferably Al ³⁺ ) and / or side subgroups of the 2nd, 7th or 8th group (preferably Zn ²⁺ , Mn ²⁺ , Fe ²⁺ , Fe ³⁺ ) of the periodic system.

Preferably, a salt or mixture of salts of phosphinic acid of the general formula (IV) is used,

in which M ^{m +} is a metal cation of the main subgroup of the 1st group (alkali metals, m = 1), the main subgroup of the 2nd group (alkaline earth metals, m = 2), or the main subgroup of the 3rd group (m = 3) or side subgroups of the 2nd, 7th or 8th group (where m is an integer from 1 to 6, preferably from 1 to 3, and particularly preferably 2 or 3) of the periodic system.

Particularly preferred for formula (IV) are:

for m = 1 metal cations M ⁺ = Li ⁺ , Na ⁺ , K ⁺ ,

for m = 2, metal cations M ²⁺ = Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , and

for m = 3 metal cations M ³⁺ = Al ³⁺ ,

highly preferred are Ca ²⁺ (m = 2) and Al ³⁺ (m = 3).

In a preferred embodiment, the average particle size d ₅₀ for the phosphinic acid salt (component D) is less than 80 microns, preferably less than 60 microns, particularly preferably d ₅₀ is between 10 microns and 55 microns. The average particle size d ₅₀ is a diameter in which case 50% of the particles have a larger value and 50% a correspondingly smaller value. Mixtures of salts that differ in their average particle size d ₅₀ may also be used.

These requirements for particle size d ₅₀ salts of phosphinic acid in each case are associated with the technical effect, namely, that increases the fire retardant efficiency of the phosphine salt.

The phosphinic acid salt can be used either individually or in combination with other phosphorus-containing flame retardants. Preferably, the compositions of the invention do not contain phosphorus-containing flame retardants represented by a group of mono- or oligomeric esters of phosphoric or phosphonic acids, phosphonamines, as well as phosphazenes. These other phosphorus-containing flame retardants, such as, for example, mono- or oligomeric esters of phosphoric or phosphonic acids, in comparison with salts of phosphinic acid, have the disadvantage that they reduce the heat resistance of the molding materials.

Component E

Component E includes one or more thermoplastic vinyl (co) polymers E.1.

Suitable vinyl (co) polymerizates of E.1 are those of at least one monomer from the group of vinyl aromatic compounds, vinyl cyanides (unsaturated nitriles), alkyl esters of (meth) acrylic acid with from 1 to 8 carbon atoms in the alkyl, unsaturated carboxylic acids, as well as derivatives (such as anhydrides and imides) of unsaturated carboxylic acids. First of all, (co) polymerizates containing:

E.1.1 from 50 to 99, preferably from 60 to 80 mass. parts of vinyl aromatic compounds and / or vinyl aromatic compounds substituted at the core, such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene and / or (meth) acrylic acid alkyl esters, with the number of carbon atoms in the alkyl from 1 to 8, such as methyl methacrylate, ethyl methacrylate, and

E.1.2 from 1 to 50, preferably from 20 to 40 mass. parts of vinyl cyanides (unsaturated nitriles), such as acrylonitrile and methacrylonitrile, and / or (meth) acrylic acid alkyl esters, having from 1 to 8 carbon atoms in the alkyl, such as methylmethacrylate, n-butyl acrylate, tert-butyl acrylate, and / or unsaturated carboxylic acids, such as maleic acid, and / or derivatives, such as anhydrides and imides, unsaturated carboxylic acids, for example, maleic anhydride and N-phenylmaleiminimide.

Vinyl (co) polymerizates of E.1 are resinous, thermoplastic and do not contain rubbers. Especially preferred is a copolymerizate of styrene as E.1.1 and acrylonitrile as E.1.2.

(Co) polymerizates corresponding to E.1 are known and can be obtained by radical polymerization, in particular by emulsion, suspension, solution polymerization or bulk polymerization methods. These (co) polymerizates preferably have an average molecular weight Mw (weight average determined by light scattering or sedimentation method) between 15,000 and 200,000.

Component F

The composition may contain other conventional additives corresponding to component F), such as flame retardant synergists, anti-dropping agents during combustion (German antidrip-pingmittel) (for example, fluorinated polyolefin compounds, silicones, and aramid fibers), lubricants and additives to facilitate removal from the form (e.g., pentaerythritetetrastearate), crystallization nuclei, stabilizers, antistatic agents (e.g., conductive carbon black, carbon fiber, carbon nanotubes, and organic antistatic agents such as polyalkylene ethers, alkylsulfonates or poliamidsoderzhaschie polymers), acids, fillers and reinforcing agents (e.g., glass or carbon fiber, mica, kaolin, talc, _CaCO3 and glass flakes) as well as dyes and pigments, . The fluorinated polyolefins are preferably used in the form of coagulated mixtures of emulsions of fluorinated polyolefins with emulsions of the vinyl (co) polymerizate E.1, particularly preferably with styrene-acrylonitrile copolymer emulsions.

Obtaining molding materials and molded products

The thermoplastic molding compositions according to the invention are obtained by mixing the respective components in a known manner and subjecting them to melt compaction and melt extrusion at temperatures from 260 ° C to 300 ° C in conventional plants such as closed plasticizers, extruders and twin screw extruders.

The mixing of the individual components can be carried out according to the known method both sequentially and in parallel, and at the same time both at a temperature of about 20 ° C (at room temperature) and at a higher temperature.

Objects of the invention are also a method for producing molding materials and the use of these molding materials for the manufacture of molded products, as well as molded parts themselves.

The molding materials according to the invention can be used for the manufacture of molded products of any kind. They can be made by injection molding, extrusion, or blow molding. Another form of processing is the manufacture of molded products by deep drawing from prefabricated plates or sheets.

Examples of such molded products are films, profiles, parts of casings of any kind, for example, for household items such as televisions, juicers, coffee machines, mixers; for electronic and computer equipment, such as monitors, flat screens, laptops, printers, copiers; plates, pipes, wiring ducts, windows, doors and other profiles for the construction sector (for interior decoration and outdoor use), as well as for electrical and electronic components such as switches, plugs and sockets, as well as body and interior structural elements for vehicles funds, primarily in the automotive industry.

In particular, the molding materials according to the invention can also be used, for example, for the manufacture of the following molded products or molded parts: interior fittings for railway vehicles, ships, airplanes, buses and other trackless vehicles, cases of electrical appliances containing low power transformers, instrument cases for the processing and transmission of information, cases and covers for medical devices, massage devices and cases for them, toy cars for children, flat FIR wall elements, housings for safety devices for televisions, heat-insulating transportable containers, moldings for medical and bathing accessories protective gratings for ventilation openings and housings for garden equipment.

The following Examples serve to further explain the invention in more detail.

Examples

Component A

Linear bisphenol-A-based polycarbonate with a relative solution viscosity η _rel = 1.315 ± 0.05, measured in CH ₂ Cl ₂ as a solvent at 25 ° C and a concentration of 0.5 g / 100 ml.

Component B-1

Linear polyethylene terephthalate having a melt viscosity of 275 Pa · s according to DIN 54811 at 265 ° C and a shear rate of 500 s ^-1 (In-vista RT-6012, INVISTA Resins & Fibers GmbH, Hatterscheim am Mein, Germany).

Component B-2

Linear polybutylene terephthalate having a melt viscosity of 622 Pa · s according to DIN 54811 at 240 ° C and a shear rate of 500 s ^-1 (In-vista RT-6012, INVISTA Resins & Fibers GmbH, Hatterscheim am Mein, Germany).

Component C

The grafted ABS copolymerizate obtained by emulsion polymerization from 43% of the mass, in terms of the ABS polymer, of a mixture consisting of 27% of the mass. acrylonitrile and 73% of the mass. styrene in the presence of 57 wt. -%, in terms of ABS polymer, granular polymer crosslinked polybutadiene rubber (average particle diameter d ₅₀ is from 0.3 to 0.4 microns).

Component D

Component D-1 (for comparison)

Bisphenol-A Oligophosphate

Component D-2

Calcium phosphinate, average particle size d ₅₀ = 50 μm

Component F

Component F-1: Coagulated mixture of emulsions of fluorinated polyolefins with emulsions of a styrene-acrylonitrile copolymerizate (Blendex® 449 from Chemtura).

Component F-2: Pentaerythritetetrastearate

Component F-3: Irganox B900 (manufacturer: Ciba Specialty Chemicals Inc., Basel, Switzerland).

Production and testing of molding compounds

Using a twin-screw extruder (ZSK-25) (Werner und Pfleiderer), the starting components listed in table 1 were subjected to compounding at a speed of 225 rpm and a capacity of 18 kg / h, as well as at a plant temperature of 260 ° C and granulation.

The finished granulate was processed using an injection molding machine into the appropriate test samples (mass temperature 260 ° C, temperature in the forming cavity 80 ° C, melt front flow rate 240 mm / s).

Characterization was carried out in accordance with ISO 527-11-2. (tensile modulus, E), ISO 306 (Vicat softening temperature, method B at a load of 50 N and a heating rate of 120 K / h), ISO 75-1 / -2 (thermal deformation temperature, HDT from the English Heat Distortion Temperature, Af method with a bending stress of 1.80 MPa and Bf method with a bending stress of 0.45 MPa), as well as UL 94 V for sample plates 3.0 mm and 1.5 mm thick.

From table 1 it is seen that only the compositions according to the invention from examples 4, 5, 6 and 10, 11, 12, containing a combination of polycarbonate, polyester and calcium phosphinate, are the solution to the problem of the present invention, that is, they give a combination of a high modulus elasticity E, high heat resistance, as well as good performance when testing for flammability according to UL 94 V.

Claims (17)

1. A molding composition comprising:
A) from 41 to 97 wt. parts (in each case, in terms of the sum of the mass parts of components A + B + C + D) of aromatic polycarbonate,
B) from 2 to 19 wt. parts (in each case, in terms of the sum of the mass parts of components A + B + C + D) of polyalkylene terephthalate,
C) from 0.5 to 15 wt. parts (in each case, in terms of the sum of the mass parts of components A + B + C + D) of the grafted copolymer modified with rubber,
D) from 0.5 to 25 wt. parts (in each case, in terms of the sum of the mass parts of components A + B + C + D) of a salt or mixture of salts of phosphinic acid of the formula (IV)

wherein
M ^{m +} is a metal cation of the main subgroup of the 1st group (alkali metals, m = 1), the main subgroup of the 2nd group (alkaline earth metals, m = 2), or the main subgroup of the 3rd group (m = 3), or side subgroups of the 2nd, 7th or 8th group (with m denoting an integer from 1 to 6) of the Periodic system. 2. The molding composition according to claim 1, containing from 4 to 17 wt. parts (in each case, in terms of the sum of the mass parts of components A + B + C + D) of polyalkylene terephthalate, as component B). 3. The molding composition according to claim 1, containing from 7 to 12 wt. parts (in each case in terms of the sum of the mass parts of components A + B + C + D) phosphinic acid salts as component D). 4. The molding composition according to claim 1, containing from 5 to 9 wt. parts (in each case, in terms of the sum of the mass parts of components A + B + C + D) of the grafted rubber modified copolymerizate as component C). 5. The molding composition according to one of claims 1 to 4, containing up to 20 wt. parts (provided that the sum of the mass parts of the components A + B + C + D = 100) not containing rubber vinyl (co) polymerizate as component E). 6. The molding composition according to one of claims 1 to 4, containing from 1 to 15 wt. parts (provided that the sum of the mass parts of the components A + B + C + D = 100) not containing rubber vinyl (co) polymerizate as component E). 7. The molding composition according to one of claims 1 to 4, containing up to 50 wt. parts (in each case, provided that the sum of the mass parts of the components A + B + C + D = 100) additives as component F). 8. The molding composition according to one of claims 1 to 4, containing as component C) one or more grafted copolymerizates from:
C.1 from 5 to 95 wt.% At least one vinyl monomer grafted onto
C.2 95 to 5% by weight of at least one graft copolymerization base selected from the following group: diene rubbers, EP (D) M rubbers, i.e. rubbers based on an ethylene / propylene mixture, and also, if necessary, a diene , acrylate, polyurethane, silicone, silicone acrylate, chloroprene, as well as ethylene / vinyl acetate rubbers. 9. The molding composition of claim 8, containing as C.1 a mixture consisting of:
C.1.1 from 50 to 99 wt. parts of vinyl aromatic and / or substituted in the core vinyl aromatic compounds, as well as
C.1.2 from 1 to 50 wt. parts of vinyl cyanides and / or derivatives of unsaturated carboxylic acids. 10. The molding composition according to one of claims 1 to 4, containing as component B) polyethylene terephthalate, polybutylene terephthalate and / or polytrimethylene terephthalate. 11. The molding composition according to one of claims 1 to 4, containing as component D) a salt or a mixture of salts of phosphinic acid, the metal cation being Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Sr ^{2 +} , Ba ²⁺ , Al ³⁺ , Zn ²⁺ , Mn ²⁺ , Fe ²⁺ and / or Fe ³⁺ . 12. The molding composition according to claim 1, wherein M ^{m +} = Ca ²⁺ and m = 2 or M ^{m +} = Al ³⁺ and m = 3. 13. The molding composition according to one of claims 1 to 4, wherein the average particle size d ₅₀ for the phosphinic acid salt (component C) is less than 80 microns. 14. The molding composition according to one of claims 1 to 4, moreover, it is free from phosphorus-containing flame retardants represented by a group of mono- or oligomeric esters of phosphoric or phosphonic acids, phosphonamines, as well as phosphazenes. 15. The molding composition according to claim 7, wherein the additives corresponding to component F) are flame retardant synergists, anti-dropping agents during combustion, lubricants and additives to facilitate removal from the mold, crystallization nuclei, stabilizers, antistatic agents, acids, fillers and enhancing agents, as well as dyes and pigments. 16. A molded product containing a molding composition according to one of claims 1 to 15. 17. The molded product according to clause 16, characterized in that it is part of a trackless vehicle, railway transport, aircraft or means of water transport or films, profile or parts of casings of any kind.